CN108275649A - A kind of MEMS combustible gas sensors and its processing method - Google Patents

A kind of MEMS combustible gas sensors and its processing method Download PDF

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Publication number
CN108275649A
CN108275649A CN201810220145.0A CN201810220145A CN108275649A CN 108275649 A CN108275649 A CN 108275649A CN 201810220145 A CN201810220145 A CN 201810220145A CN 108275649 A CN108275649 A CN 108275649A
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metal catalyst
precious metal
layer
catalyst layer
mems
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CN108275649B (en
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沈方平
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Suzhou Tantalum Krypton Electronic Technology Co Ltd
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Suzhou Tantalum Krypton Electronic Technology Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B81MICROSTRUCTURAL TECHNOLOGY
    • B81BMICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
    • B81B7/00Microstructural systems; Auxiliary parts of microstructural devices or systems
    • B81B7/02Microstructural systems; Auxiliary parts of microstructural devices or systems containing distinct electrical or optical devices of particular relevance for their function, e.g. microelectro-mechanical systems [MEMS]
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B81MICROSTRUCTURAL TECHNOLOGY
    • B81CPROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C1/00Manufacture or treatment of devices or systems in or on a substrate
    • B81C1/00349Creating layers of material on a substrate
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B81MICROSTRUCTURAL TECHNOLOGY
    • B81BMICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
    • B81B2201/00Specific applications of microelectromechanical systems
    • B81B2201/02Sensors
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B81MICROSTRUCTURAL TECHNOLOGY
    • B81BMICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
    • B81B2201/00Specific applications of microelectromechanical systems
    • B81B2201/02Sensors
    • B81B2201/0292Sensors not provided for in B81B2201/0207 - B81B2201/0285
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

A kind of MEMS combustible gas sensors of present invention offer and its processing method, including silicon base, the lower surface of silicon base is equipped with 2 insulated tanks, upper surface is equipped with heat insulation layer, adiabatic layer surface is equipped with the first precious metal catalyst layer and the second precious metal catalyst layer symmetrical and for porous structure, first precious metal catalyst layer and the second precious metal catalyst layer are located at the surface of 2 insulated tanks, first precious metal catalyst layer surface is equipped with gas-insulated layer, second precious metal catalyst layer surface is provided with air hole, gas-insulated layer surface is equipped with one group of reference resistor, and it connects with the first precious metal catalyst layer and the second precious metal catalyst layer, gas-insulated layer edge is equipped with several lead windows.MEMS combustible gas sensors provided by the invention are small, low in energy consumption, and performance is stablized, and processing method is simple, and production efficiency is high.

Description

A kind of MEMS combustible gas sensors and its processing method
Technical field
The invention belongs to combustible gas sensor technical fields, and in particular to a kind of MEMS combustible gas sensors and its add Work method.
Background technology
MEMS full name Micro Electromechanical System, MEMS refer to that size is at several millimeters To smaller high-tech device, internal structure is generally an independent intelligence system in micron even nanometer scale.Be Grow up on the basis of microelectric technique (semiconductor fabrication), has merged photoetching, burn into film, silicon micromachined, non-silicon The high-tech electronic mechanical devices that the technologies such as micro Process and precision machinery processing make.
Combustible gas sensor is widely used in the fields such as coal mine, domestic gas alarm, industry monitoring, security protection.With hydrogen Fuel cell car gradually moves towards the visual field of people, and combustible gas sensor also begins to enter vehicle electric field, for monitoring The leak case of fuel-hydrogen of automobile, ensures the safety of driver.Catalytic type combustible gas sensor is to utilize infusibility gold Belong to the resistance variations after platinum filament heating to measure combustable gas concentration.When fuel gas enters detector, draw on platinum filament surface Oxidation reaction (flameless combustion) is played, the heat generated makes the temperature of platinum filament increase, and the resistance of platinum filament just changes, according to The variation of resistance can calculate the concentration of gas.
Traditional catalytic combustion gas sensor bulk is big, high energy consumption, adds man-hour requirement hand-made, complex process is raw It is low to produce efficiency, and artificial production has prodigious error, the performance for being easy to cause sensor unstable.
Invention content
The purpose of the present invention is the deficiency for existing catalytic combustion gas sensor, provide it is a kind of small, it is low in energy consumption, Performance is stablized, and processing method is simple, the high MEMS combustible gas sensors of production efficiency and its processing method.
The present invention provides the following technical solutions:
The lower surface of a kind of MEMS combustible gas sensors, including silicon base, the silicon base is equipped with 2 insulated tanks, on Surface is equipped with heat insulation layer, and the thermal insulation layer surface is equipped with the first precious metal catalyst layer and second symmetrical and for porous structure Precious metal catalyst layer, the first precious metal catalyst layer and the second precious metal catalyst layer are being located at 2 insulated tanks just Top, the first precious metal catalyst layer surface are equipped with gas-insulated layer, and the second precious metal catalyst layer surface is provided with ventilative Hole, the gas-insulated layer surface be equipped with one group of reference resistor, and with the first precious metal catalyst layer and described second your gold Belong to Catalytic Layer series connection, the gas-insulated layer edge is equipped with several lead windows.
Preferably, it is anti-to be equipped with first for the lower surface of the first precious metal catalyst layer and the second precious metal catalyst layer Oxide buffer layers, the first precious metal catalyst layer are equipped with the second anti-oxidant buffer layer with the gas-insulated interlayer.
Preferably, the described first anti-oxidant buffer layer and the second anti-oxidant buffer layer are titanium nitride, tantalum nitride, oxidation One or several kinds in titanium, aluminium oxide, zirconium oxide, tungsten oxide, yttrium oxide and vanadium oxide.
Preferably, the temperature coefficient of the reference resistor is less than 50PPM/ DEG C.
Preferably, the resistance of the reference resistor is the first precious metal catalyst layer and the second precious metal catalyst layer 100-1000 times.
Preferably, the reference resistor is titanium nitride or tantalum nitride.
Preferably, the first precious metal catalyst layer and the second precious metal catalyst layer are platinum, palladium or platinum-nickel alloys, thickness Degree is 400nm-3000nm.
A kind of processing method of MEMS combustible gas sensors, includes the following steps:
S1:Cleaning silicon base simultaneously dries up, heavy with Low Pressure Chemical Vapor Deposition and plasma enhanced chemical vapor respectively Area method is sequentially depositing one layer of silicon nitride and layer of silicon dioxide in silicon substrate surface, obtains the heat insulation layer of 1-5 μ m-thicks;
S2:One group of symmetrical precious metal catalyst layer and graphical is deposited in adiabatic layer surface with magnetron sputtering method, by moving back Fire processing obtains the first precious metal catalyst layer and the second precious metal catalyst layer of porous structure;
S3:In the surface deposited silicon nitride and silica of the first precious metal catalyst layer and the second precious metal catalyst layer, shape At the gas-insulated layer of 600-4000nm thickness, air hole is etched above the second precious metal catalyst layer with counter ion etching method, Go out several lead windows in the etching edge of gas-insulated layer;
S4:With the technique in S2 a pair of of reference resistor is deposited in gas-insulated layer surface;
S5:The technique being combined using wet method and dry method prepares insulated tank below silicon base.
Preferably, the upper and lower surface of the first precious metal catalyst layer and the second precious metal catalyst layer is splashed with magnetic control in the S2 It penetrates method and deposits anti-oxidant buffer layer, the first precious metal catalyst layer and the second precious metal catalyst layer can directly connect or pass through circuit Series connection.
Preferably, the treatment temperature of magnetron sputtering method is 650-1100 DEG C in the S2, and processing time is 10 minutes -3 small When.
The beneficial effects of the invention are as follows:
(1) present invention employs the preparations of the MEMS processing methods of planarization, are sensed compared to traditional catalytic combustion gas Device, MEMS combustible gas sensors provided by the invention, volume greatly reduce, and power consumption is reduced to milliwatt rank by a watt grade, therefore Service life is long.
(2) MEMS combustible gas sensors provided by the invention, precious metal catalyst layer are made in the method for magnetron sputtering, phase Than the heating coil that traditional filament-winding method makes, processing method is simple, and stability greatly promotes.
(3) processing method of MEMS combustible gas sensors provided by the invention, easy to operate, production efficiency is high.
Description of the drawings
Attached drawing is used to provide further understanding of the present invention, and a part for constitution instruction, the reality with the present invention It applies example to be used to explain the present invention together, not be construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the main structure diagram of the present invention;
Fig. 2 is the overlooking structure diagram of the present invention.
In figure label for:1, silicon base;2, insulated tank;3, heat insulation layer;4, the first anti-oxidant buffer layer;5, the first noble metal Catalytic Layer;6, the second anti-oxidant buffer layer;7, gas-insulated layer;8, the second precious metal catalyst layer;9, lead window;10, it breathes freely Hole;11, reference resistor.
Specific implementation mode
As depicted in figs. 1 and 2, a kind of MEMS combustible gas sensors, including silicon base 1, the lower surface of silicon base 1 are equipped with 2 insulated tanks 2, upper surface are equipped with heat insulation layer 3, and 3 surface of heat insulation layer is equipped with the first noble metal symmetrical and for porous structure Catalytic Layer 5 and the second precious metal catalyst layer 8, the first precious metal catalyst layer 5 and the second precious metal catalyst layer 8 are located at 2 absolutely The surface of heat channel 2,5 surface of the first precious metal catalyst layer are equipped with gas-insulated layer 7, and 8 surface of the second precious metal catalyst layer is provided with Air hole 10,7 surface of gas-insulated layer be equipped with one group of reference resistor 11, and with the first precious metal catalyst layer 5 and the second noble metal Catalytic Layer 8 is connected, and the temperature coefficient of reference resistor is less than 50PPM/ DEG C, and 7 edge of gas-insulated layer is equipped with several lead windows 9.
The lower surface of first precious metal catalyst layer 5 and the second precious metal catalyst layer 8 is equipped with the first anti-oxidant buffer layer 4, The second anti-oxidant buffer layer 6 is equipped between first precious metal catalyst layer 5 and gas-insulated layer 7.
The operation principle of the present invention is that:First precious metal catalyst layer 5, the second precious metal catalyst layer 8 and a pair of of reference resistor 11 constitute Wheatstone bridge, when applying voltage at electric bridge both ends, the first precious metal catalyst layer 5 and the second precious metal catalyst layer 8 Due to Joule heat temperature rise, the second precious metal catalyst layer 8 is catalyzed gas fuel burning, and the heat for generation of burning keeps its temperature high In the first precious metal catalyst layer 5, leads to Wheatstone bridge disequilibrium and obtain voltage signal, the voltage value and fuel gas Concentration is in a linear relationship, to obtain combustable gas concentration.
Embodiment 1
A kind of processing method of MEMS combustible gas sensors, includes the following steps:
S1:Cleaning silicon base simultaneously dries up, heavy with Low Pressure Chemical Vapor Deposition and plasma enhanced chemical vapor respectively Area method is sequentially depositing one layer of silicon nitride and layer of silicon dioxide in silicon substrate surface, obtains the heat insulation layer of 1 μ m-thick;
S2:The first anti-oxidant buffer layer of one layer of titanium nitride material is deposited in adiabatic layer surface with magnetron sputtering method, then The precious metal catalyst layer of one group of symmetrical alloy platinum material and graphical is deposited in the same way, and porous knot is obtained by annealing Structure, thickness be 400nm the first precious metal catalyst layer and the second precious metal catalyst layer, treatment temperature be 650 DEG C, processing time It is 3 hours, the second anti-oxidant buffer layer of one layer of tantalum-nitride material of subsequent redeposition;
S3:In the second anti-oxidant buffer-layer surface deposited silicon nitride and silica, the gas-insulated of 600nm thickness is formed Layer, etches air hole above the second precious metal catalyst layer with counter ion etching method, goes out in the etching edge of gas-insulated layer Several lead windows;
S4:The reference resistor of a pair of of titanium nitride material, resistance are deposited in gas-insulated layer surface with the technique in S2 It is 100 times of the first precious metal catalyst layer and the second precious metal catalyst layer;
S5:The technique being combined using wet method and dry method prepares insulated tank below silicon base, you can obtaining MEMS can Combustion gas body sensor.
Embodiment 2
A kind of processing method of MEMS combustible gas sensors, includes the following steps:
S1:Cleaning silicon base simultaneously dries up, heavy with Low Pressure Chemical Vapor Deposition and plasma enhanced chemical vapor respectively Area method is sequentially depositing one layer of silicon nitride and layer of silicon dioxide in silicon substrate surface, obtains the heat insulation layer of 5 μ m-thicks;
S2:The precious metal catalyst layer and figure of one group of symmetrical palladium material are deposited in adiabatic layer surface with magnetron sputtering method Change, by making annealing treatment the first precious metal catalyst layer and the second precious metal catalyst that obtain porous structure, that thickness is 3000nm Layer, treatment temperature are 1100 DEG C, and processing time is 10 minutes;
S3:In the surface deposited silicon nitride and silica of the first precious metal catalyst layer and the second precious metal catalyst layer, shape At the gas-insulated layer of 4000nm thickness, air hole is etched above the second precious metal catalyst layer with counter ion etching method, in gas The etching edge of body isolation layer goes out several lead windows;
S4:The reference resistor of a pair of of tantalum-nitride material, resistance are deposited in gas-insulated layer surface with the technique in S2 It is 1000 times of the first precious metal catalyst layer and the second precious metal catalyst layer;
S5:The technique being combined using wet method and dry method prepares insulated tank below silicon base, you can obtaining MEMS can Combustion gas body sensor.
Embodiment 3
A kind of processing method of MEMS combustible gas sensors, includes the following steps:
S1:Cleaning silicon base simultaneously dries up, heavy with Low Pressure Chemical Vapor Deposition and plasma enhanced chemical vapor respectively Area method is sequentially depositing one layer of silicon nitride and layer of silicon dioxide in silicon substrate surface, obtains the heat insulation layer of 3 μ m-thicks;
S2:Resisted the first of one layer of titanium oxide of adiabatic layer surface deposition, aluminium oxide and zirconia material with magnetron sputtering method Then oxide buffer layers deposit the precious metal catalyst layer of one group of symmetrical platinum-nickel alloys material and graphical in the same way, By making annealing treatment the first precious metal catalyst layer and the second precious metal catalyst layer that obtain porous structure, that thickness is 2000nm, Treatment temperature is 900 DEG C, and processing time is 1.5 hours, then redeposition tungsten oxide layer, yttrium oxide and vanadium oxide material the Secondary antibody oxide buffer layers;
S3:In the second anti-oxidant buffer-layer surface deposited silicon nitride and silica, the gas-insulated of 2500nm thickness is formed Layer, etches air hole above the second precious metal catalyst layer with counter ion etching method, goes out in the etching edge of gas-insulated layer Several lead windows;
S4:A pair of of reference resistor is deposited in gas-insulated layer surface with the technique in S2, resistance is the first noble metal 500 times of Catalytic Layer and the second precious metal catalyst layer;
S5:The technique being combined using wet method and dry method prepares insulated tank below silicon base, you can obtaining MEMS can Combustion gas body sensor.
The MEMS combustible gas sensors that embodiment 1-3 is prepared, compared with conventional catalyst burning gases sensor, work( Consumption reduces by 10 times, is reduced within 50Mw by 500Mw, and the response time was reduced to 3 seconds by 6 seconds, and measurement range promotes one times, by 0- 4% is promoted to 0-8%.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, although with reference to aforementioned reality Applying example, invention is explained in detail, for those skilled in the art, still can be to aforementioned each implementation Technical solution recorded in example is modified or equivalent replacement of some of the technical features.All essences in the present invention With within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention god.

Claims (10)

1. a kind of MEMS combustible gas sensors, which is characterized in that including silicon base, the lower surface of the silicon base is equipped with 2 Insulated tank, upper surface are equipped with heat insulation layer, and the thermal insulation layer surface is equipped with symmetrical and is urged for the first noble metal of porous structure Change layer and the second precious metal catalyst layer, the first precious metal catalyst layer and the second precious metal catalyst layer are located at described in 2 The surface of insulated tank, the first precious metal catalyst layer surface are equipped with gas-insulated layer, the second precious metal catalyst layer table Face is provided with air hole, and the gas-insulated layer surface is equipped with one group of reference resistor, and with the first precious metal catalyst layer and institute The series connection of the second precious metal catalyst layer is stated, the gas-insulated layer edge is equipped with several lead windows.
2. a kind of MEMS combustible gas sensors according to claim 1, which is characterized in that first precious metal catalyst The lower surface of layer and the second precious metal catalyst layer is equipped with the first anti-oxidant buffer layer, the first precious metal catalyst layer with The gas-insulated interlayer is equipped with the second anti-oxidant buffer layer.
3. a kind of MEMS combustible gas sensors according to claim 2, which is characterized in that the first anti-oxidant buffering Layer and the described second anti-oxidant buffer layer be titanium nitride, tantalum nitride, titanium oxide, aluminium oxide, zirconium oxide, tungsten oxide, yttrium oxide and One or several kinds in vanadium oxide.
4. a kind of MEMS combustible gas sensors according to claim 1, which is characterized in that the temperature of the reference resistor Coefficient is less than 50PPM/ DEG C.
5. a kind of MEMS combustible gas sensors according to claim 4, which is characterized in that the resistance of the reference resistor Resistance value is 100-1000 times of the first precious metal catalyst layer and the second precious metal catalyst layer.
6. a kind of MEMS combustible gas sensors according to claim 5, which is characterized in that the reference resistor is nitridation Titanium or tantalum nitride.
7. a kind of MEMS combustible gas sensors according to claim 1, which is characterized in that first precious metal catalyst Layer and the second precious metal catalyst layer are platinum, palladium or platinum-nickel alloys, thickness 400nm-3000nm.
8. a kind of processing method of MEMS combustible gas sensors, which is characterized in that include the following steps:
S1:Cleaning silicon base simultaneously dries up, respectively with Low Pressure Chemical Vapor Deposition and plasma enhanced chemical vapor deposition method, It is sequentially depositing one layer of silicon nitride and layer of silicon dioxide in silicon substrate surface, obtains the heat insulation layer of 1-5 μ m-thicks;
S2:One group of symmetrical precious metal catalyst layer and graphical is deposited in adiabatic layer surface with magnetron sputtering method, at annealing Reason obtains the first precious metal catalyst layer and the second precious metal catalyst layer of porous structure;
S3:In the surface deposited silicon nitride and silica of the first precious metal catalyst layer and the second precious metal catalyst layer, formed The gas-insulated layer of 600-4000nm thickness etches air hole with counter ion etching method above the second precious metal catalyst layer, The etching edge of gas-insulated layer goes out several lead windows;
S4:With the technique in S2 a pair of of reference resistor is deposited in gas-insulated layer surface;
S5:The technique being combined using wet method and dry method prepares insulated tank below silicon base.
9. a kind of processing method of MEMS combustible gas sensors according to claim 8, which is characterized in that in the S2 The upper and lower surface of first precious metal catalyst layer and the second precious metal catalyst layer deposits anti-oxidant buffer layer with magnetron sputtering method, the One precious metal catalyst layer and the second precious metal catalyst layer can directly connect or be connected by circuit.
10. a kind of processing method of MEMS combustible gas sensors according to claim 8, which is characterized in that the S2 The treatment temperature of middle magnetron sputtering method is 650-1100 DEG C, and processing time is -3 hours 10 minutes.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109970022A (en) * 2019-04-01 2019-07-05 深圳邺诚科技有限公司 A kind of MEMS catalytic combustion sensor and its processing method
CN112782338A (en) * 2020-12-28 2021-05-11 苏州芯镁信电子科技有限公司 Explosion-proof structure for gas sensor, preparation method and packaging method thereof
WO2022052392A1 (en) * 2020-09-08 2022-03-17 苏州芯镁信电子科技有限公司 Side-heating type silicon-based thin film catalytic hydrogen sensor and processing method therefor

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CN105987935A (en) * 2015-02-16 2016-10-05 郑州炜盛电子科技有限公司 Mems gas sensor and manufacturing method thereof
CN106770585A (en) * 2016-12-16 2017-05-31 苏州钽氪电子科技有限公司 A kind of MEMS solid electrolytes oxygen sensor and its processing method
CN207957757U (en) * 2018-03-16 2018-10-12 苏州钽氪电子科技有限公司 A kind of MEMS combustible gas sensors

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WO2022052392A1 (en) * 2020-09-08 2022-03-17 苏州芯镁信电子科技有限公司 Side-heating type silicon-based thin film catalytic hydrogen sensor and processing method therefor
CN112782338A (en) * 2020-12-28 2021-05-11 苏州芯镁信电子科技有限公司 Explosion-proof structure for gas sensor, preparation method and packaging method thereof

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